Research Group n. 4
UNIVERSITA’ DEGLI STUDI DI PISA
Organometallic and Coordination compounds of Transition Elements:
Preparation, Reactivity and Applications
Fabio Marchetti,a Fabio Marchetti,b Guido Pampaloni, Filippo Renili
, Born in Bologna in 1974, b Born in Castelfiorentino (FI) in 1950
Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, I-56126 Pisa; E-mail:
The research involves: i) the synthesis of derivatives of transition elements containing
polyfunctional quinones; ii) the study of the activation of oxygen ligands by early transition
metal halides; iii) metal complexes as precursors of functionalized inorganic matrices.
i) Work has been done concerning complexes of 1,10-phenanthroline-5,6-dione of Groups 4, 5
and 6 elements. We have found that 1,10-phenanthroline-5,6-dione is a useful starting material
for the preparation of mono-, bi- and polynuclear compounds due to the presence of quinonoid
and iminic functionalities on the same molecule. Work in this field will be continued aiming to
the preparation of oligo- and heterometallic compounds containing polyfunctional quinones as
bridging ligands, and to study their electronic and magnetic properties.
ii) The coordination chemistry of the halides MX5 (M = Nb, Ta) with oxygen donor ligands has
been scarcely developed heretofore. Recently, a variety of coordination compounds of this type
has been prepared. The reactions must be carried out in strictly anhydrous conditions, and the
products have been identified by means of IR and NMR spectroscopies, and X ray diffraction.
The first step of these reactions is the simple coordination of the ligand to the metal. Hence, in
some cases, some activation can take place. The target of this investigation is to extend the
series of coordination compounds of MX5 with O-donor ligands, and to exploit the possibility to
obtain functionalized organic molecules.
iii) The implantation of metals on a solid matrix has attracted considerable interest in the last
decades for the properties and implications in industrial processes of the resulting materials.
Different methods can be used for the supportation on inorganic matrixes: the most common
starts from metal hydrides or alkyls, or from low-valent transition metal derivatives such as
metal carbonyls. In the framework of this research topic, we recently became interested in the
implantation of Group 4 and 5 metals on silica surfaces in the form of metal N,N-
dialkylcarbamates M(O2CNR2)n. The latter is a class of compounds recently used for the
implantation of Sn(IV), late transition metals, and lanthanides on a surface of partially
Keywords: Metal Complexes, quinones, metal halides, oxygenated ligands, implantation, silica,
Detailed list of the components of the research groups
1. F. Marchetti, G. Pampaloni, S. Zacchini, Reactivity of Niobium(V) and Tantalum(V) Halides with Carbonyl Compounds:
Synthesis of Simple Coordination Adducts, C–H bond Activation, C=O Protonation, and Halide Transfer, Dalton Trans., 2007,
2. L. Calucci, U. Englert, L. Margheriti, G. Pampaloni, C. Pinzino, A. Prescimone, 1,10-Phenanthroline-5,6-dione Complexes of
Middle Transition Elements: Mono- and Dinuclear Derivatives, Inorg. Chim. Acta, 2008, 361, 2375.
3. F. Marchetti, G. Pampaloni and S. Zacchini, From 1,2-Dialkoxyalkanes to 1,4-Dioxanes. A Transformation Mediated by NbCl5 via
Multiple C–O Bond Cleavage at Room Temperature, Chem. Commun, 2008, 3651.
4. F. Marchetti, G. Pampaloni, S. Zacchini, The Reactivity of 1,1-Dialkoxyalkanes with Niobium and Tantalum Pentahalides.
Formation of Coordination Compounds, C–H and C–C Bonds Activation and the X-Ray Structure of the Stable Carboxonium
Species [Me2C=CHC(=OMe)Me][NbCl5(OMe)], Dalton Trans., 2009, 8096.
5. L. Calucci, C. Forte, G. Pampaloni, C. Pinzino, F. Renili, Chemical Implantation of Group 4 Cations on Silica via
Cyclopentadienyl- and N,N-Dialkylcarbamato Derivatives, Inorg. Chim. Acta, 2010, 363, 33.
6. R. Bini, C. Chiappe, F. Marchetti, S. Zacchini, G. Pampaloni, The Structures and the Unusual Rearrangements of Coordination
Adducts of MX5 (M = Nb, Ta; X = F, Cl) with Simple Diethers. A Crystallographic, Spectroscopic and Computational Study,
Inorg. Chem., 2010, 49, 339.
(permanent staff, included graduated students and postdocs)
Name Surname Position * Affiliation
Guido Pampaloni PA Università di Pisa
Fabio ** Marchetti RU Università di Pisa
Fabio*** Marchetti PA Università di Pisa
Filippo Renili PhD Università di Pisa
*: PO = full professor; PA = associated professor; RU = university researcher; PhD = graduated
student; PoD = postdoctoral fellows; RC = CNR staff; T = technician
** Born in Bologna in 1974
*** Born in Castelfiorentino (FI) in 1950
(minimum value 25.000 € per item)
Type Producer Year of
NMR Spectrometer Varian Gemini 200BB Varian 1992
NMR Bruker Avance DRX 400 Spectrometer for Bruker 2009
high resolution and solid state spectra
Bruker AXS P4 Diffractometer Bruker 1995
Bruker AXS D8 Powder Diffractometer Bruker 2002
FTIR spectrometer Spectrum One with ATR PerkinElmer 2005
FTIR spectrometer Spectrum 100 with extended PerkinElmer 2009
range (7800-225 cm1)
Stirred high pressure reactor 300 mL with Parr Instrument Company 2009
Microscope SteREO Discovery.V8 supplied with Zeiss 2008
• Synthesis and characterization of organometallic and coordination compounds.
• Study of the reactivity of organometallic and coordination compounds.